Nonlinear modelling of non-structural masonry walls under a low-intensity earthquake motion: calibration through a parametric study

This thesis aims to understand the behavior of a low-rise unreinforced masonry building (URM), the typical residential house in the Netherlands, when subjected to low-intensity earthquakes. In fact, in the last decades, the Groningen region was hit by several shallow earthquakes caused by the extraction of natural gas. In particular, the focus is addressed to the internal non-structural walls and to their interaction with the structural parts of the building. A simple and cost-efficient 2D FEM model is developed, focused on the interfaces representing mortar layers that are present between the non-structural walls and the rest of the structure. As a reference for geometries and materials, it has been taken into consideration a prototype that was built in full-scale at the EUCENTRE laboratory of Pavia (Italy). Firstly, a quasi-static analysis is performed by gradually applying a prescribed displacement on the roof floor of the structure. Sensitivity analyses are conducted on some key parameters characterizing mortar. This analysis allows for the calibration of their values and the evaluation of the reliability of the model. Successively, a transient analysis is performed to effectively subject the model to a seismic action and hence also evaluate the mechanical response of the building over time. Moreover, it was possible to compare the results of this analysis with the displacements recorded in the experimental tests by creating a model representing the entire considered structure. As a result, some conditions for the model calibration are defined. The reliability of the model is then confirmed by both the reasonable results obtained from the sensitivity analysis and the compatibility of the values obtained for the top displacement of the roof floor of the experimental test, and the same value acquired from the structural model.

Calibration of the detector flight models for the HERMES and SPIRIT nanosatellite missions

The High Energy Rapid Modular Ensemble of Satellites (HERMES) is a new mission concept involving the development of a constellation of six CubeSats in low Earth orbit with new miniaturized instruments that host a hybrid Silicon Drift Detector/GAGG:Ce based system for X-ray and γ-ray detection, aiming to monitor high-energy cosmic transients, such as Gamma Ray Bursts and the electromagnetic counterparts of gravitational wave events. The HERMES constellation will also operate together with the Australian-Italian SpIRIT mission, which will house a HERMES-like detector. The HERMES pathfinder mini-constellation, consisting of six satellites plus SpIRIT, is likely to be launched in 2023. The HERMES detectors are based on the heritage of the Italian ReDSoX collaboration, with joint design and production by INFN-Trieste and Fondazione Bruno Kessler, and the involvement of several Italian research institutes and universities. An application-specific, low-noise, low-power integrated circuit (ASIC) called LYRA was conceived and designed for the HERMES readout electronics. My thesis project focuses on the ground calibrations of the first HERMES and SpIRIT flight detectors, with a performance assessment and characterization of the detectors. The first part of this work addresses measurements and experimental tests on laboratory prototypes of the HERMES detectors and their front-end electronics, while the second part is based on the design of the experimental setup for flight detector calibrations and related functional tests for data acquisition, as well as the development of the calibration software. In more detail, the calibration parameters (such as the gain of each detector channel) are determined using measurements with radioactive sources, performed at different operating temperatures between -20°C and +20°C by placing the detector in a suitable climate chamber. The final part of the thesis involves the analysis of the calibration data and a discussion of the results.

Analysis of human posterior EEG alpha frequency as a function of implicit learning of probabilistic lateralized stimuli in a visual detection task

Alpha oscillatory activity has long been associated with perceptual and cognitive processes related to attention control. The aim of this study is to explore the task-dependent role of alpha frequency in a lateralized visuo-spatial detection task. Specifically, the thesis focuses on consolidating the scientific literature's knowledge about the role of alpha frequency in perceptual accuracy, and deepening the understanding of what determines trial-by-trial fluctuations of alpha parameters and how these fluctuations influence overall task performance. The hypotheses, confirmed empirically, were that different implicit strategies are put in place based on the task context, in order to maximize performance with optimal resource distribution (namely alpha frequency, associated positively with performance): “Lateralization” of the attentive resources towards one hemifield should be associated with higher alpha frequency difference between contralateral and ipsilateral hemisphere; “Distribution” of the attentive resources across hemifields should be associated with lower alpha frequency difference between hemispheres; These strategies, used by the participants according to their brain capabilities, have proven themselves adaptive or maladaptive depending on the different tasks to which they have been set: "Distribution" of the attentive resources seemed to be the best strategy when the distribution probability between hemifields was balanced: i.e. the neutral condition task. "Lateralization" of the attentive resources seemed to be more effective when the distribution probability between hemifields was biased towards one hemifield: i.e., the biased condition task.

Development and Automatization of a Planar Jet Wind Tunnel for the X-wire Calibration

The scope of this study is to design an automatic control system and create an automatic x-wire calibrator for a facility named Plane Air Tunnel; whose exit creates planar jet flow. The controlling power state as well as automatic speed adjustment of the inverter has been achieved. Thus, the wind tunnel can be run with respect to any desired speed and the x-wire can automatically be calibrated at that speed. To achieve that, VI programming using the LabView environment was learned, to acquire the pressure and temperature, and to calculate the velocity based on the acquisition data thanks to a pitot-static tube. Furthermore, communication with the inverter to give the commands for power on/off and speed control was also done using the LabView VI coding environment. The connection of the computer to the inverter was achieved by the proper cabling using DAQmx Analog/Digital (A/D) input/output (I/O). Moreover, the pressure profile along the streamwise direction of the plane air tunnel was studied. Pressure tappings and a multichannel pressure scanner were used to acquire the pressure values at different locations. Thanks to that, the aerodynamic efficiency of the contraction ratio was observed, and the pressure behavior was related to the velocity at the exit section. Furthermore, the control of the speed was accomplished by implementing a closed-loop PI controller on the LabView environment with and without using a pitot-static tube thanks to the pressure behavior information. The responses of the two controllers were analyzed and commented on by giving suggestions. In addition, hot wire experiments were performed to calibrate automatically and investigate the velocity profile of a turbulent planar jet. To be able to analyze the results, the physics of turbulent planar jet flow was studied. The fundamental terms, the methods used in the derivation of the equations, velocity profile, shear stress behavior, and the effect of vorticity were reviewed.

Calibration of design strength values of Wire and Arc Additive Manufacturing inclined bars and intersections

Although being studied only for few years, Wire and Arc Additive Manufacturing (WAAM) will become the predominant way of producing stainless-steel elements in a near-like future. The analysis and study of such elements has yet to be defined in a proper way, but the projects regarding this subject are innovating more and more thanks to the findings discovered by the latter. This thesis is focused on an initial stage on the analysis of mechanical and geometrical properties of such stainless-steel elements produced by MX3D laboratories in Amsterdam, and to perform a calibration of the design strength values by means of Annex D of Eurocode 0, which talks about the analysis of the semi-probabilistic safety factors, hence the definition of characteristic values. Moreover, after testing the stainless-steel specimens by means of strain gauges and after obtaining mechanical and geometrical properties, a statistical analysis of such properties and an evaluation of characteristic values is performed. After this, there is to execute the calibration of design strength values of WAAM inclined bars and intersections.

A Highly Improved Method For Sensitive Determination Of Amitriptyline In Pharmaceutical Formulations Using An Unmodified Carbon Nanotube Electrode In The Presence Of Sulfuric Acid.

The present paper describes a novel, simple and reliable differential pulse voltammetric method for determining amitriptyline (AMT) in pharmaceutical formulations. It has been described for many authors that this antidepressant is electrochemically inactive at carbon electrodes. However, the procedure proposed herein consisted in electrochemically oxidizing AMT at an unmodified carbon nanotube paste electrode in the presence of 0.1 mol L(-1) sulfuric acid used as electrolyte. At such concentration, the acid facilitated the AMT electroxidation through one-electron transfer at 1.33 V vs. Ag/AgCl, as observed by the augmentation of peak current. Concerning optimized conditions (modulation time 5 ms, scan rate 90 mV s(-1), and pulse amplitude 120 mV) a linear calibration curve was constructed in the range of 0.0-30.0 μmol L(-1), with a correlation coefficient of 0.9991 and a limit of detection of 1.61 μmol L(-1). The procedure was successfully validated for intra- and inter-day precision and accuracy. Moreover, its feasibility was assessed through analysis of commercial pharmaceutical formulations and it has been compared to the UV-vis spectrophotometric method used as standard analytical technique recommended by the Brazilian Pharmacopoeia.

Propylthiouracil Quantification In Human Plasma By High-performance Liquid Chromatography Coupled With Electrospray Tandem Mass Spectrometry: Application In A Bioequivalence Study.

A rapid, sensitive and specific method for quantifying propylthiouracil in human plasma using methylthiouracil as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by liquid-liquid extraction using an organic solvent (ethyl acetate). The extracts were analyzed by high performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC-MS/MS) in negative mode (ES-). Chromatography was performed using a Phenomenex Gemini C18 5μm analytical column (4.6mm×150mm i.d.) and a mobile phase consisting of methanol/water/acetonitrile (40/40/20, v/v/v)+0.1% of formic acid. For propylthiouracil and I.S., the optimized parameters of the declustering potential, collision energy and collision exit potential were -60 (V), -26 (eV) and -5 (V), respectively. The method had a chromatographic run time of 2.5min and a linear calibration curve over the range 20-5000ng/mL. The limit of quantification was 20ng/mL. The stability tests indicated no significant degradation. This HPLC-MS/MS procedure was used to assess the bioequivalence of two propylthiouracil 100mg tablet formulations in healthy volunteers of both sexes in fasted and fed state. The geometric mean and 90% confidence interval CI of Test/Reference percent ratios were, without and with food, respectively: 109.28% (103.63-115.25%) and 115.60% (109.03-122.58%) for Cmax, 103.31% (100.74-105.96%) and 103.40% (101.03-105.84) for AUClast. This method offers advantages over those previously reported, in terms of both a simple liquid-liquid extraction without clean-up procedures, as well as a faster run time (2.5min). The LOQ of 20ng/mL is well suited for pharmacokinetic studies. The assay performance results indicate that the method is precise and accurate enough for the routine determination of the propylthiouracil in human plasma. The test formulation with and without food was bioequivalent to reference formulation. Food administration increased the Tmax and decreased the bioavailability (Cmax and AUC).

Fast And Direct Na And K Determination In Table, Marine, And Low-sodium Salts By X-ray Fluorescence And Chemometrics.

X-ray fluorescence (XRF) is a fast, low-cost, nondestructive, and truly multielement analytical technique. The objectives of this study are to quantify the amount of Na(+) and K(+) in samples of table salt (refined, marine, and light) and to compare three different methodologies of quantification using XRF. A fundamental parameter method revealed difficulties in quantifying accurately lighter elements (Z < 22). A univariate methodology based on peak area calibration is an attractive alternative, even though additional steps of data manipulation might consume some time. Quantifications were performed with good correlations for both Na (r = 0.974) and K (r = 0.992). A partial least-squares (PLS) regression method with five latent variables was very fast. Na(+) quantifications provided calibration errors lower than 16% and a correlation of 0.995. Of great concern was the observation of high Na(+) levels in low-sodium salts. The presented application may be performed in a fast and multielement fashion, in accordance with Green Chemistry specifications.

Diretrizes curriculares nacionais para o ensino médio: avaliação de documento

This text offers some contributions to the debate on the changes proposed to the National Curricular Directives to reform secondary education in Brazil. In the first part, the political and economic scene is evaluated as the context which generated the last stage of reforms in the educational field in the 90s. It questions the option for a model of structural reform (in the Brazilian case more restricted to the Program for Reform of Professional Education - PROEP) and of the curriculum, whose themes find their justification in the contemporary economic, social cultural and political context. It discusses the use of a model that bases itself on experiences developed in other countries and takes the international orientation of the multilateral organizations as its theoretical methodological reference, leaving out the peculiarities and injunctions of the Brazilian political administrative system. Such a policy measure can increase the tension and distance normally existing between government programs and the possibility of their real implementation in the school network. In the second part, it discusses the Resolution of the National Education Council, the Congress on Basic Education, no.3, of 16.698 that instituted the National Curricular Directives for secondary education, as well as the Legal Bases - Part I - of the National Curricular Parameters for secondary education. The analysis of official discourse takes Bardin's (1977, p. 209) proposals as its methodological reference for the models of structural analysis, seeking to make the implicit values and the connotations of the legal texts explicit

PARAFAC: uma ferramenta quimiométrica para tratamento de dados multidimensionais. Aplicações na determinação direta de fármacos em plasma humano por espectrofluorimetria

Since the last decade, the combined use of chemometrics and molecular spectroscopic techniques has become a new alternative for direct drug determination, without the need of physical separation. Among the new methodologies developed, the application of PARAFAC in the decomposition of spectrofluorimetric data should be highlighted. The first objective of this article is to describe the theoretical basis of PARAFAC. For this purpose, a discussion about the order of chemometric methods used in multivariate calibration and the development of multi-dimensional methods is presented first. The other objective of this article is to divulge for the Brazilian chemical community the potential of the combination PARAFAC/spectrofluorimetry for the determination of drugs in complex biological matrices. For this purpose, two applications aiming at determining, respectively, doxorrubicine and salicylate in human plasma are presented.

25 anos de quimiometria no Brasil

Chemometric activities in Brazil are described according to three phases: before the existence of microcomputers in the 1970s, through the initial stages of microcomputer use in the 1980s and during the years of extensive microcomputer applications of the ´90s and into this century. Pioneering activities in both the university and industry are emphasized. Active research areas in chemometrics are cited including experimental design, pattern recognition and classification, curve resolution for complex systems and multivariate calibration. New trends in chemometrics, especially higher order methods for treating data, are emphasized.

Aplicação de métodos de calibração multivariada para a determinação simultânea de riboflavina (VB2), tiamina (VB1), piridoxina (VB6) e nicotinamida (VPP)

In this work, the artificial neural networks (ANN) and partial least squares (PLS) regression were applied to UV spectral data for quantitative determination of thiamin hydrochloride (VB1), riboflavin phosphate (VB2), pyridoxine hydrochloride (VB6) and nicotinamide (VPP) in pharmaceutical samples. For calibration purposes, commercial samples in 0.2 mol L-1 acetate buffer (pH 4.0) were employed as standards. The concentration ranges used in the calibration step were: 0.1 - 7.5 mg L-1 for VB1, 0.1 - 3.0 mg L-1 for VB2, 0.1 - 3.0 mg L-1 for VB6 and 0.4 - 30.0 mg L-1 for VPP. From the results it is possible to verify that both methods can be successfully applied for these determinations. The similar error values were obtained by using neural network or PLS methods. The proposed methodology is simple, rapid and can be easily used in quality control laboratories.

Estado da arte de figuras de mérito em calibração multivariada

The validation of an analytical procedure must be certified through the determination of parameters known as figures of merit. For first order data, the acuracy, precision, robustness and bias is similar to the methods of univariate calibration. Linearity, sensitivity, signal to noise ratio, adjustment, selectivity and confidence intervals need different approaches, specific for multivariate data. Selectivity and signal to noise ratio are more critical and they only can be estimated by means of the calculation of the net analyte signal. In second order calibration, some differentes approaches are necessary due to data structure.

Construção de um calorímetro isotérmico diferencial de alta sensibilidade e baixo custo

The high cost of sensitivity commercial calorimeters may represent an obstacle for many calorimetric research groups. This work describes the construction and calibration of a batch differential heat conduction calorimeter with sample cells volumes of about 400 μL. The calorimeter was built using two small high sensibility square Peltier thermoelectric sensors and the total cost was estimated to be about US$ 500. The calorimeter was used to study the excess enthalpy of solution of binary mixtures of liquids, as a function of composition, for the following binary systems of solvents: water + 1,4-dioxane or + dimethylsulfoxide at 298,2 ± 0,5 K.

Estatística aplicada à química: dez dúvidas comuns

Ten common doubts of chemistry students and professionals about their statistical applications are discussed. The use of the N-1 denominator instead of N is described for the standard deviation. The statistical meaning of the denominators of the root mean square error of calibration (RMSEC) and root mean square error of validation (RMSEV) are given for researchers using multivariate calibration methods. The reason why scientists and engineers use the average instead of the median is explained. Several problematic aspects about regression and correlation are treated. The popular use of triplicate experiments in teaching and research laboratories is seen to have its origin in statistical confidence intervals. Nonparametric statistics and bootstrapping methods round out the discussion.